초임계 Tetrahydrofuran을 이용한 Polystyrene의 분획

김형진; 박경애; 정일현; 홍인권

Journal of the Korean Industrial and Engineering Chemistry, Vol.6, No.1, 155-164, February, 1995

Export Citation

초임계 Tetrahydrofuran을 이용한 Polystyrene의 분획

Fractionation of Polystyrene using Supercritical Tetrahydrofuran

김형진, 박경애, 정일현, 홍인권

초록

기능성 고분자 제조에는 여러 가지 방법이 있으나 본 연구에서는 다분산 고분자 물질을 단분산화시키는 '용매 추출 분획' 방법에 이론적 배경을 두고 연구하였다. 온도와 압력 조절이 가능한 고압반응기에 0.5w/v%로 용해된 polystyrene용액을 충진하고 THF의 임계온도(T_c=540.2K)와 임계압력(P_c=752.64psi) 이상에서 같은 농도의 용액을 정량펌프를 이용해 20m1/min으로 공급하여 반응기의 압력을 일정한 간격으로 증가시키면서 연속적으로 시료를 추출하고 추출된 시료를 GPC로 분석하였다. 분석한 결과를 토대로 Schulz분포 함수를 이용해 분자량별로 연속 분포함수를 표현하였다. 또한 UV-vis. spectrophotometer를 이용하여 각 압력에서 추출된 시료의 농도를 측정하여 분자량에 대한 누적 무게 분율을 도시하였다. 본 연구에의 결과에 의하면 polystyrene의 녹는점(533.15K) 이상에서 분획이 잘됨을 알 수 있었고, 녹는점 이상인 548.15K에서 압력이 증가함에 따라 추출된 고분자의 분자량은 증가하고 분산도는 감소함을 알 수 있었다. 그러나 polystyrene의 녹는점 이하인 518.15K에서는 압력 증감에 따른 추출된 고분자의 분자량과 분산도와의 관계는 그 의존성이 작게 나타남을 알 수 있었다.

There are many methods for manufacturing of functional polymer, but solvent elusion fractionation is the theoretical background which can obtain the monodisperse polymer from the polydisperse polymer in this study. The high pressure reactor which can tune temperature and pressure was filled with 0.5w/v% polystyrene solution, and the same concentration solution was feed to reactor at the rate of 20m11min using a metering pump above critical pressure of tetrahydrofuran. The extracted samples of each pressure were collected continuously and analyzed by GPC. Continuous distribution function was predicted as a function of molecular weight using a Schulz' distribution function on the basis of acquired data. Also, cumulative weight fraction was predicted as a function of molecular weight on the basis of concentration data of sample which was obtained by UV-vis. spectrophotometer. It was predicted that the fractionation efficiency was improved, and molecular weight of extract was increased and polydispersity was decreased with increasing pressure above the melting temperature of polystyrene. But molecular weight of extract and polydispersity had small dependency on pressure below the melting temperature of polystyrene.

[References]

Bright FV, "Supercritical Fluid Technology," 1-2, American Chemical Society, Washington (1992)
McHugh MA, Krukonis VJ, "Supercritical Fluid Extraction," 192-258, Butterworth-Heinemann (1994)
Iwai Y, Yamamoto H, Sohda M, Tanaka Y, Shimizu T, Arai Y, Memoris Faculty Eng., 49, 175 (1989)
Desimone JM, Guan Z, Elsbernd CS, Science, 257, 945 (1992)
Berens AR, Hurand GS, Korsmeyer RW, AIChE Meet., 48b (1988)
Cantow MJ, "Polymer Fractionation," 379-413, Academic Press, N.Y. (1967)
Kurata M, "Thermodynamics of Polymer Solutions," 118, Harwood Academic Publishers, N.Y. (1982)
Willman B, Teja AS, Ind. Eng. Chem. Res., 26, 948 (1987)
Willman B, Teja AS, Ind. Eng. Chem. Process Des. Dev., 24, 1033 (1985)
Cotterman RL, Prausnitz JM, Ind. Eng. Chem. Process Des. Dev., 24, 434 (1985)
Tung LH, J. Polym. Sci., 20, 495 (1956)
Lansing WD, Kraemer EO, J. Am. Chem. Soc., 57, 1369 (1935)
Schulz GV, Z. Phys. Chem., B43, 25 (1939)
Tung LH, "Fractionation of Synthetic Polymers-Principles and Practices," 489-531, Marcel Dekker Inc., N.Y. (1977)
Kumar SK, Chhabria SP, Reid RC, Suter UW, Macromolecules, 20, 2550 (1987)

[Referenced By]

[1] Bright FV, "Supercritical Fluid Technology," 1-2, American Chemical Society, Washington (1992)

[2] McHugh MA, Krukonis VJ, "Supercritical Fluid Extraction," 192-258, Butterworth-Heinemann (1994)

[3] Iwai Y, Yamamoto H, Sohda M, Tanaka Y, Shimizu T, Arai Y, Memoris Faculty Eng., 49, 175 (1989)

[4] Desimone JM, Guan Z, Elsbernd CS, Science, 257, 945 (1992)

[5] Berens AR, Hurand GS, Korsmeyer RW, AIChE Meet., 48b (1988)

[6] Cantow MJ, "Polymer Fractionation," 379-413, Academic Press, N.Y. (1967)

[7] Kurata M, "Thermodynamics of Polymer Solutions," 118, Harwood Academic Publishers, N.Y. (1982)

[8] Willman B, Teja AS, Ind. Eng. Chem. Res., 26, 948 (1987)

[9] Willman B, Teja AS, Ind. Eng. Chem. Process Des. Dev., 24, 1033 (1985)

[10] Cotterman RL, Prausnitz JM, Ind. Eng. Chem. Process Des. Dev., 24, 434 (1985)

[11] Tung LH, J. Polym. Sci., 20, 495 (1956)

[12] Lansing WD, Kraemer EO, J. Am. Chem. Soc., 57, 1369 (1935)

[13] Schulz GV, Z. Phys. Chem., B43, 25 (1939)

[14] Tung LH, "Fractionation of Synthetic Polymers-Principles and Practices," 489-531, Marcel Dekker Inc., N.Y. (1977)

[15] Kumar SK, Chhabria SP, Reid RC, Suter UW, Macromolecules, 20, 2550 (1987)